Higher Symmetry Multinuclear Clusters of MOFs for Highly Selective

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Higher Symmetry Multinuclear Clusters of MOFs for Highly Selective CO2 Capture Jingjing Jiang, Zhiyong Lu, Mingxing Zhang, Jingui Duan, Wenwei Zhang, Yi Pan, and Junfeng Bai J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b07589 • Publication Date (Web): 18 Sep 2018 Downloaded from http://pubs.acs.org on September 18, 2018

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Journal of the American Chemical Society

Higher Symmetry Multinuclear Clusters of MOFs for Highly Selective CO2 Capture Jingjing Jianga‡, Zhiyong Luc‡, Mingxing Zhanga, Jingui Duand, Wenwei Zhanga, Yi Pana, Junfeng Bai*a,b a

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China b School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China c College of Mechanics and Materials, Hohai University, Nanjing 210098, China. d State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 210009, China. Supporting Information Placeholder ABSTRACT: A new approach of finely tuning multinuclear clusters of MOFs through symmetry-upgradingly isoreticular transformation was firstly presented and a bcu-type MOF, {[Cu4(µ4-O)Cl2(IN)8]•CuCl2}∞ (NJU-Bai35; NJU-Bai for Nanjing University Bai group), with cluster [Cu4(µ4-O)(COO)4N4Cl2] of higher symmetry compared to the pristine MOF, was successfully synthesized. The symmetry upgrading implemented on the inorganic part triggers the adjustment of channels in NJU-Bai35 to fit CO2 molecules, leading to a high CO2 adsorption capacity (7.20 wt% at ~ 0.15 bar and 298 K) and high selectivity of CO2 over N2 and CH4 (275.8 for CO2/N2 and 11.6 for CO2/CH4) in NJU-Bai35. Breakthrough experiments further confirmed that NJU-Bai35 might be an excellent candidate for CO2 capture and natural gas purification.

Global warming is one of our greatest concerns due to the rapid growth of CO2 emission.1 To reduce CO2 emission, great efforts have been devoted to the development of diverse CO2 capture materials, in which many porous solids have been intensively investigated. Metal-organic frameworks (MOFs), due to their intriguing and controllable structures, are regarded as a promising kind of material for CO2 capture.2 Very recently, much work is focused on enhancing the selective gas-adsorption performances of MOFs by finely tuning their structures and inner environment in which almost six strategies have been evolved based upon isoreticular synthesis.2i, 3 Through isoreticular synthesis, initiated by Yaghi’s group,4 a series of typical MOFs have been constructed by many groups.5-9 Much work has been devoted on the variation of organic parts, such as ligand extension,5 ligand functionalization,6 ligand geometry variation7 as well as coordination-sites shifting.8 Due to the strong controllability of organic synthesis, modification of organic parts in MOFs is much more predictable and fruitful. In contrast, for the inorganic moiety which is strongly correlated to the topology of MOFs, its variation generally leads to a topological change, and therefore, seldom successful examples were reported till now except some isostructural MOFs substituted by different metal ions.9 In particular, isoreticular synthesis of MOFs by finely tuning the inorganic moieties remains a great challenge.

Herein, we present a new apporach of finely tuning multinuclear clusters through symmetry-upgradingly isoreticular transformation towards MOFs with highly selective CO2 uptake from a simple bitopic ligand, isonicotinic acid (IN). Taking the advantage of great variability of inorganic clusters in bcu-type MOF, we chose {[Cu2(IN)8]•DMF}∞ (FZU, for Fuzhou University) with binuclear clusters as a precursor for isoreticular transformation.10 Through solvent-change and temperature-elevation, we gradually increased the complexity of inorganic clusters and optimized the symmetry of them as well, and the precursor transformed to an isoreticular structure with clusters of higher symmetry, {[Cu4(µ4O)Cl2(IN)8]•CuCl2}∞ (NJU-Bai35). Very interestingly, the symmetry upgrading of inorganic clusters triggered the adjustment of channels in NJU-Bai35 to a proper size for CO2 molecules, which leads to high CO2 uptake capacity as well as CO2 selectivity. It is the first example of achieving high selective CO2 uptake by upgrading the symmetry of inorganic clusters in isoreticular MOFs. FZU has one-dimensional channels of about 4.0 × 4.0 Å2 along a axis. Every pair of Cu atoms is bridged by two carboxylate moieties from two independent ligands to form a binuclear cupric cluster (Fig. 1a). There are two uncoordinated O atoms from carboxylate groups in the cupric cluster and the binuclear cluster is not robust from a mechanical perspective, which may induce a structural flexibility. The uncoordinated O atoms provide the possibility of incorporating extra metal ions for increasing the complexity of inorganic clusters while upgrading the symmetry of them without changing their connectivity, by which the porosity of MOFs could be finely tuned.

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Figure 1. Isoreticular transformation of bcu-type MOF by symmetry-upgrading inorganic clusters. a), b), and c) are inorganic clusters of FZU, NJU-Bai34, and NJUBai35, respectively; d), e), and f) are structures of FZU, NJU-Bai34, and NJU-Bai35 viewed along a axis. Green dash lines in every cluster are presented to help understand the eight-connectivity of clusters (eight vertices of either regular cube or distorted cube).

Our assumption was realized by increasing the concentration of Cu2+ ions and adding H2O, CH3CN, and CH3COOH, and then an isoreticular robust {[Cu4(IN)8(µ3-O)2(CH3COO)2]•NH2(CH3)2} ∞ (NJU-Bai34, in Fig. 1e) constructed by a more complex cluster [Cu4(µ3-O)2(COO)4N4O2] was synthesized. The cluster in NJUBai34 contains four Cu atoms without any uncoordinated O atoms from carboxylate groups (Fig. 1b). All Cu atoms in this new cluster adopt five-coordinated geometry. Without incorporating extra ligands, the rest coordination sites on Cu atoms are saturated by CH3COO-. Therefore, this new cluster still links with eight IN ligands but exhibits an optimized geometry compared with the clusters in FZU. Unlike FZU with obvious channels only along a axis, the geometry optimization of inorganic clusters makes the channels along b and c axis accessible, with the sizes of 3.3 × 7.2 Å2 and 4.0 × 4.0 Å2, respectively (Fig. S3). Meanwhile, in NJUBai34, the size of channels along a axis remains (Fig. 1e). However, due to the coordination of CH3COO-, ((CH3)2NH2)+ derived from the hydrolysis of DMF was needed to keep the whole structure neutral. Thus, parts of the channels are blocked by the coordinated CH3COO- and its counter ions, as illustrated in Fig. S4. To avoid the coordination of CH3COO-, we further changed the solvent system to DMF/H2O and rose the temperature to 120 °C. Cl atoms rooting in CuCl2•2H2O began to participate in the coordination and made the four Cu atoms much more contracted compared with those in NJU-Bai34’s cluster. This unprecedented cluster, [Cu4(µ4-O)(COO)4N4Cl2] along with IN ligand further assembles into NJU-Bai35. This contraction upgraded the symmetry of inorganic cluster from Ci point group to D2 point group without causing any variation of connectivity. Therefore, the whole structure still adopts a bcu-net. The symmetry upgrading of inorganic

cluster consequently improves the steric configuration of whole structure, and the channels along every direction turn into a more even dimension, with the sizes of 3.6 × 3.6, 3.4 × 3.4, 3.6 × 3.6 Å2 along a, b, and c axis which are quite suitable for CO2 molecules. Meanwhile, such a symmetry upgrading endows a higher rigidity of NJU-Bai35, which can be confirmed by its VT-PXRD patterns in Fig. S15c. Without the participation of CH3COO- and other solvent molecules in coordination, channels along a and b axis are actually occupied by CuCl2 in as-synthesized NJU-Bai35. However, after a long period of methanol-exchange, CuCl2 can be totally removed and then all the channels in the activated sample could be exposed to gas molecules.

Figure 2. Possible mechanism in the process of symmetry-upgradingly isoreticular transformation

Meanwhile, it is interesting to note that FZU can change into NJU-Bai34 and NJU-Bai34 could subsequently transform to NJUBai35 under specific conditions. NJU-Bai35 can also be directly transformed from FZU. The transformation process is not reversi-


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Journal of the American Chemical Society ble (Figure 2). The experimental details are shown in Section 3 in Supporting Information (SI). As shown in Figure 2 and Section 3 in SI, the mechanism underlying from FZU to NJU-Bai34 (or NJU-Bai35) might be: 1) more Cu2+ ions coordinate with the uncoordinated O atoms in the cluster of FZU; 2) H2O molecules act as µ3-O in NJU-Bai34 playing the role of linking three adjacent Cu atoms and locking them in the tetranuclear inorganic cluster and act as µ4-O in NJU-Bai35 connecting four Cu atoms in the cluster; 3) CH3COOH molecules (or Cl- ions) serve as terminal coordinated molecules to eliminate extra coordination number increased by new-incorporated Cu atoms, which is essential in keeping the new synthesized structure isoreticular to the original one. NJU-Bai35 may be a thermodynamic product and the addition of CH3COOH benefits the formation of NJU-Bai34, which is regarded as a kinetic product. CH3COOH can be a competitor of Cl- in coordination with Cu atoms, and the addition of CH3CN can help CH3COOH win the game of getting pure NJU-Bai34.

Figure 3. For FZU, NJU-Bai34, and NJU-Bai35. a) N2 adsorption isotherms at 77 K; b) CO2 adsorption isotherms measured at 298 K; c) CO2 selectivity calculated by IAST; d) Breakthrough curves of NJU-Bai35 that are initially saturated with CO2.

In order to investigate the effect of isoreticular symmetry upgrading on gas adsorption, we measured the N2 adsorption of the three analogues (Fig. 3a). The BET surface areas of FZU, NJUBai34, and NJU-Bai35 were calculated to be 332.7 m2 g-1, 362.2 m2 g-1, and 862.8 m2 g-1, respectively. Clearly, by exposing channels in every direction via symmetry upgrading, the surface of these channels could be more accessible to gas molecules and thus NJU-Bai35 shows the highest surface area. The CO2 adsorption capacities of FZU, NJU-Bai34, and NJUBai35 were further investigated. As shown in Fig. 3b, at 298 K, NJU-Bai35 exhibits apparently the highest CO2 adsorption capacity. At a relatively low pressure (∼0.15 bar, a typical partial pressure for CO2 in flue gases), the CO2 uptake of NJU-Bai35 is 7.20 wt%, which is much higher than that of NJU-Bai34 (2.67 wt%) and FZU (2.01 wt%). Meanwhile, this uptake capacity is quite

comparable with that of NJU-Bai78a (8.0 wt%), and as well higher than that of some MOFs with open metal sites or functional groups, such as Cu-TDPAT11 (7.13 wt%), Fe-BTT12 (5.3 wt%), and ZIF-7813 (3.3 wt%). Initially, we attributed the high CO2 adsorption capacity of NJU-Bai35 to the sole factor of its high BET surface area. However, such perspective is not convincible with the example of NJU-Bai34 with higher surface area showing lower CO2 capacity at high-pressure range than FZU but comparably higher uptake capacity at low-pressure range. For a better interpretation of the CO2 adsorption mechanisms, we further calculated their CO2 adsorption enthalpies (Fig. S19). The zero-coverage CO2 adsorption enthalpy of NJU-Bai35 is 33.37 kJ mol-1, which is obviously higher than that of FZU (30.64 kJ mol-1) and NJUBai34 (30.71 kJ mol-1). Even among the whole range of loading, NJU-Bai35 is the highest. Without any open metal sites, the high CO2 adsorption enthalpy in NJU-Bai35 should be attributed to the



suitable pore sizes which are more suitable for CO2 accommodation. Combined with its relatively high BET surface area, a high CO2 uptake capacity was therefore found in NJU-Bai35. Notably, there is a slight steep in the CO2 isotherm of FZU at ~ 0.12 bar (Fig. 3b & Fig. S21), which indicates that FZU is flexible. This characteristic is supported by the evidence of steep in Ar isotherm (Fig. S20) and peak shifting in PXRD pattern of FZU (Fig. S14a & Fig. S15a). It is the pore expansion in FZU during the adsorption process that helps FZU accommodating more CO2 molecules than NJU-Bai34 in high-pressure range. Table 1. BET surface areas, CO2 uptakes, enthalpies, and selectivities of FZU, NJU-Bai34, and NJU-Bai35 at 298 K MOFs

BET

CO2 uptakea

Qst, CO2

CO2/CH4

(wt %)

FZU

332.7

2.01

30.64

28.3

4.3

NJU-Bai34

362.2

2.67

30.71

60.1

8.2

NJU-Bai35

862.8

7.20

33.37

275.8

11.6

a

(kJ mol-1)

CO2/N2

(m2g-1)

data at 0.15 bar and 298 K

After upgrading the symmetry of inorganic moiety, the great improvement of CO2 adsorption in NJU-Bai35 may indicate a high CO2 selectivity. Therefore, the CO2 selectivities of the three analogues were calculated by using Ideal Adsorbed Solution Theory (IAST), as shown in Table 1. Due to the flexibility of FZU, the contracted form of FZU shows a lower CO2 uptake but higher CH4 and N2 uptakes compared with NJU-Bai34. Therefore, the CO2 selectivity of NJU-Bai34 is much higher than that of FZU. NJU-Bai35 with the highest CO2 uptake exhibits the highest CO2 selectivity among the three analogues, with the values of 275.8 for CO2/N2 and 11.6 for CO2/CH4. These values are also larger than those of SIFSIX-2-Cu-I3b (CO2/N2, 140), Cu-TDPAT11 (CO2/N2, 79; CO2/CH4, 5.3), and ZIF-7813 (CO2/N2, 50.1; CO2/CH4, 10.6) under similar conditions. Such high CO2 selectivities should be attributed to molecule sieving effect in NJU-Bai35, whose pore sizes are more suitable for CO2 (3.3 Å) than N2 (3.64 Å) and CH4 (3.8 Å) molecules. The high selective CO2 capture of NJU-Bai35 was further confirmed by breakthrough experiments. The breakthrough curve at 298 K for a 2 : 8 mixture of CO2 and N2 (5 : 5 mixture of CO2 and CH4) in Fig. 3d shows that CO2 is completely separated from N2 (or CH4) with a considerable CO2 separation capacity (44 cm3 g-1 for CO2 : N2 = 2 : 8; 59 cm3 g-1 for CO2 : CH4 = 5 : 5)-a value close to the uptake of CO2 (42 cm3 g-1 at 0.2 bar and 58 cm3 g-1 at 0.5 bar) from the single-component isotherms. The breakthrough experiments indicate that under mixture flow, NJU-Bai35 primarily adsorbs CO2, consistent with the IAST results. In summary, by an unprecedented approach of upgrading the symmetry of inorganic clusters, a new bcu-type MOF, NJUBai35, was successfully synthesized. Very interestingly, NJUBai35 shows significantly high CO2 adsorption capacity as well as CO2 selectivity, which indicates that it may be a very promising candidate for post-combustion carbon capture and the purification of natural gas. In addition, the gradual transformation from FZU to NJU-Bai35 is also the first example of symmetry-upgradingly isoreticular transformation. Our work presents a comparably green strategy for finely-tuning of MOFs independent of exhausting organic syntheses. It reveals a novel aspect of the isoreticular chemistry and is also an excellent complement for it. This new strategy may further facilitate optimization of MOFs towards high performance in the future application.

ASSOCIATED CONTENT

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Supporting Information Syntheses of MOFs, single-crystal structures, gas sorption measurements, IAST calculations, breakthrough experiments. The Supporting Information is available free of charge on the ACS Publications website.

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected], [email protected].

Author Contributions ‡ J. J. and Z. L. contributed equally.

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT We acknowledge Cheung Kong Scholars Program, the Hundred Talents Program of Shaanxi Province, and the National Natural Science Foundation of China (21771121 and 21601047) for their supports. Ms. J. Jiang is in debt to the support of the program B for outstanding PhD candidate of Nanjing University (201702B050). In addition, we would like to thank Prof. Omar M. Yaghi for his valuable suggestion on the title of this paper.

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Figure 1. Isoreticular transformation of bcu-type MOF by symmetry-upgrading inorganic clusters. 399x270mm (300 x 300 DPI)


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Figure 2. Possible mechanism in the process of symmetry-upgradingly isoreticular transformation 2799x1322mm (72 x 72 DPI)



Figure 3. For FZU, NJU-Bai34, and NJU-Bai35. a) N2 adsorption isotherms at 77 K; b) CO2 adsorption isotherms measured at 298 K; c) CO2 selectivity calculated by IAST; d) Breakthrough curves of NJU-Bai35 that are initially saturated with CO2. 869x629mm (96 x 96 DPI)


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Higher Symmetry Multinuclear Clusters of MOFs for Highly Selective

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